TWI640565B - Polymer latex particle composition containing nano silver particles - Google Patents

Abstract

The invention relates to a polymer latex particle composition containing nano silver particles, which comprises polymer latex particles and nano silver particles dispersed and coated on the surface of the polymer latex particles, and has an antibacterial function.

Description

Polymer latex particle composition containing nano silver particles

The present invention relates to a polymer latex particle composition containing nano silver particles, in particular to a polymer latex particle composition prepared by specific conditions, the surface of which is uniformly and firmly coated with a layer. Nano silver. Thereby, the latex particles of the invention have good antibacterial activity, can not only replace the addition of preservatives in cosmetics, but also solve the problem that tiny nano silver penetrates into the human cells through the skin, and can make the silver particles reach the nanometer. Disperse the grade to enhance its antibacterial effect.

In recent years, cosmetic care products have become an indispensable daily necessities for beauty lovers. In order to extend the life of cosmetic products, it is necessary to add chemical antibacterials or preservatives to cosmetic products to improve the shelf life. Preservatives most commonly added to cosmetic care products such as parabens, Phenoxyethanol, Benzoic acid, sorbic acid, and other organic chemicals, and It has a good antibacterial effect, but when it accumulates over a certain dose after long-term use, there are still doubts about skin allergies and toxicity.

In addition to chemically synthesized organic antibacterial agents or preservatives, the most widely known inorganic antibacterial agents are nano silver particles, which have excellent deodorizing and bactericidal effects and are resistant to high temperatures. In addition, the nano silver particles can also avoid the need to contact the absence of ultraviolet light when using titanium dioxide photocatalyst for antibacterial. According to this, there are many inventions by using nano The particles are bonded to different substrates to provide additional antimicrobial activity to the substrate.

For example, the method of manufacturing a substrate-containing surface-bonded metal nanoparticle according to the Patent Publication No. I455778 of the Republic of China, discloses a method for producing a surface-bonded metal nanoparticle of a substrate, comprising the steps of: The substrate is immersed in a salt solution containing a predetermined concentration of metal ions, the metal ions in the salt solution are attached to the substrate, the substrate is taken out, and a reaction solution containing a predetermined reducing agent is added. Adhering to the substrate, and providing an energy to the substrate, causing metal ions attached to the substrate to be reduced to metal nanoparticles, and finally, drying the substrate in a predetermined manner to obtain a bonding metal The base material of the nanoparticle, whereby the product produced is not easy to leave a chemical component harmful to the human body, and does not need to be treated by a complicated separation procedure; the Republic of China Patent Publication No. I495481 "Polyoxime composite particles and The manufacturing method and the cosmetic material disclose a polyfluorene-oxygen composite particle which can be added to the deodorant cosmetic, and is characterized in that 100 parts by mass of the polythene oxide elastomer spherical particles It is coated with 0.5 to 25 parts by mass of a polyoxyxene resin, wherein the polyfluorene oxide spherical particles have an average particle diameter of 0.1 to 100 μm, and the polyfluorene oxide resin has an organic germanium sesquioxane unit as a main component. Ingredients, and inorganic fine particles having an average particle diameter of 100 nm or less; and the Republic of China Patent Publication No. I455718 "Nano-silver particles/clay composites for antibacterial use and a method for producing the same", which disclose a method applicable to biology, medicine, Nano-silver particles/clay composites in the fields of chemistry, chemical engineering, materials, etc. (such as antibacterial and scald medical treatment), which are a powder, including metal particles and flaky inorganic clay, wherein the length and width of the flaky inorganic clay a ratio of 100 to 1000, and as a carrier of the metal particles, so that the metal particles reach nanometer-scale dispersion, the size of the antibacterial nano metal particles/inorganic clay composite is 5 to 100 nm; wherein the sheet-like inorganic When the clay is bentonite or nano-powder, and the flaky inorganic clay is bentonite, the weight ratio of the nano metal particles to the clay is 1:100~1:13.83 or 1:6.944~100:1; the flaky inorganic When the clay is a nano-slice, M clay particles and metal weight ratio of 1: 13.43 to 100: 1; a metal selected from the group of silver Into the group.

According to the literature search results, although there are many applications for bonding nano silver particles to different substrates, how to achieve uniform bonding of nano silver particles to a substrate depends on different preparation methods. Therefore, how to develop and produce better nano-silver particle polystyrene latex particles as an antibacterial agent is an urgent need for the inventors in related fields to break through.

The main object of the present invention is to provide a latex particle prepared by a specific condition, the surface of which is uniformly and firmly adhered and distributed with nano silver. Thereby, the latex particles obtained by the present invention have good antibacterial activity and can be added to the cosmetic as a preservative.

In order to achieve the above-mentioned object, the present invention relates to a polymer latex particle composition containing nano silver particles, which comprises polymer latex particles and nano silver particles dispersed on the surface of the polymer latex particles, wherein the polymer latex particles The diameter is greater than 50 nm, the diameter of the nano silver particles is 1 to 500 nm, and the weight percentage of the polymer latex particles and the nano silver particles is 1000:1 to 1:1.

In one embodiment of the present invention, the polymer latex particles may be, for example, polystyrene latex particles, polymethylmethacrylate latex particles, latex particles of styrene and methyl methacrylate copolymer. Latex particles of a copolymer of styrene and n-butyl methacrylate, latex particles of a copolymer of methyl methacrylate and n-butyl methacrylate.

In one embodiment of the present invention, the polymer latex particle composition containing nano silver particles has a spherical structure or an elliptical structure; if the polymer latex particles are polystyrene latex particles, the preparation method of the composition may be For example, the polystyrene latex particle suspension is uniformly mixed with an aqueous solution of silver nitrate (AgNO ₃ ) to form a mixed solution, and is allowed to act at a temperature of 90 ° C for 1 hour; and the mixed solution is cooled to 80 ° C, and then sodium citrate is added. The aqueous solution was allowed to act in the mixed solution for 0.5 hours to obtain polystyrene latex particles coated with nano silver particles; wherein the polystyrene latex particle suspension was composed of 3.8 wt% polystyrene latex particles and the remaining weight percentage Made up of water.

In an embodiment of the present invention, the polymer latex particle composition containing nano silver particles can be used for inhibiting the growth of Gram-positive bacteria, Gram-negative bacteria and fungi; thereby, the height of the silver-containing particles is high. The molecular latex particle composition can be used as a cosmetic raw material composition and a pharmaceutical composition as a bacteriostatic agent or a preservative.

First Figure: Appearance pattern of nano-silver particle-containing polystyrene latex particles prepared in accordance with one embodiment of the present invention.

Fig. 2 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the second embodiment of the present invention.

Fig. 3 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the three specific embodiments of the present invention.

Fig. 4 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by four specific embodiments of the present invention.

Fig. 5 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the fifth embodiment of the present invention.

Fig. 6 is a graph showing the inhibition concentration of the nano-silver particle polystyrene latex particles of the present invention.

The object of the present invention and its structural and functional advantages will be explained in conjunction with the specific embodiments according to the structure shown in the following drawings, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.

The invention relates to a polymer latex particle composition containing nano silver particles, which comprises polymer latex particles and nano silver particles dispersed on the surface of the polymer latex particles. The polymer latex particles have a diameter of more than 50 nm, the nano silver particles have a diameter of 1 to 500 nm, and the polymer latex particles and the nano silver particles have a weight percentage of 1000:1 to 1:1.

The polymer latex particle composition containing the nano silver particles is a spherical structure or an elliptical structure; the polymer latex particles are polystyrene latex particles, polymethylmethacrylate latex particles or polymethyl Latex particles of poly-n-butyl methacrylate, latex particles of styrene and methyl methacrylate copolymer, latex particles of styrene and n-butyl methacrylate copolymer, methyl methacrylate Latex particles copolymerized with n-butyl methacrylate, etc.; if the polymer latex particles are polystyrene latex particles, the composition can be prepared, for example, by the following method: a suspension containing polystyrene latex particles ( For example, consisting of 3.8 wt% polystyrene latex particles and residual weight percent of water) uniformly mixed with an aqueous solution of silver nitrate (AgNO ₃ ) to form a mixed solution, which is allowed to act at a temperature of 90 ° C for 1 hour; and the mixed solution is cooled to 80. °C, and then added an aqueous solution of sodium citrate in the mixed solution for 0.5 hours to obtain polystyrene latex particles coated with nano silver particles. Inhibit the bacteria (e.g., gram-positive bacteria and Gram-negative bacteria) and fungal growth ability, and therefore can be added to the raw material composition cosmetic and pharmaceutical compositions.

It is worth noting here that the inventor of the present invention applied for another application "a method for preparing nano-silver particle polymer latex particles" on the same day, which is not described in detail herein, and all of its contents are hereby incorporated by reference. .

In addition, the scope of the invention may be further exemplified by the following specific examples, which are not intended to limit the scope of the invention.

Example 1: Preparation of polystyrene latex particles

The steps of synthesizing the polystyrene latex particles are as follows: (1) first mixing 1.9 g of polyethylenimine (PEI), 30 g of methanol and 1 g of deionized water, and then placing them in a reaction tank (low speed stirring); (2) taking 0.3g initiator AIBN (Azobisisobutyronitrile) is dissolved in 15g of methanol to prepare AIBN methanol solution; (3) 10g of styrene is added to the reaction tank and stirred with the solution of step (1), and heated to 70 ° C for about 15 minutes; 4) rapidly distilling the AIBN methanol solution uniformly dissolved in the step (2) into the reaction tank, maintaining the temperature at 70 ° C for 8 hours to obtain a PS latex emulsion containing polystyrene latex particles; and (5) The polystyrene latex particles are purified by centrifugation and have an average particle diameter of more than 100 nm (about 100 to 2000 nm).

Embodiment 2

Referring to Table 1, the synthesis steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) 0.1g of silver nitrate (AgNO ₃ ) is mixed with 5g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually turns into a goose yellow solution) ), to form a mixed solution, and for 1 hour; (5) after the mixed solution is cooled to 85 ° C, then add sodium citrate aqueous solution (1.94 grams of sodium citrate dissolved in 10 grams of deionized water), continue the reaction for 10 minutes The solution is slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the average particle diameter of the nano silver particles is 5 ~100nm. For the results observed by Transmission Electron Microscopy (TEM), please refer to the first figure. After adding sodium citrate, it only reacts for 10 minutes, and the reaction time is too short, so that the amount of silver particles synthesized is too small. And the silver particles are not enough to be adsorbed on the PS latex particles, so the surface of the entire PS latex particles cannot be covered, and the surface of some PS latex particles is bare.

Table I

Embodiment 3

Referring to Table 2, the synthesis steps of the nano silver particle-containing polystyrene latex particles in this embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a suspension of polystyrene latex particles; (2) placing a uniformly mixed suspension of polystyrene latex particles in a reaction tank, raising the temperature to 90 ° C to 95 ° C without a condenser and nitrogen gas Continuous stirring; (3) 0.1 g of silver nitrate (AgNO ₃ ) is mixed with 5 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C to 95 ° C (at this time, the reaction tank solution) Will gradually become a goose yellow solution) to form a mixed solution and act for 1 hour; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (1.94 g of sodium citrate dissolved in 10 g of deionized water) ), the reaction is continued for 20 minutes to slowly turn the solution into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the nano silver particles are obtained. The average particle size is 5 to 100 nm. For the results observed by a transmission electron microscope (TEM), please refer to the second figure. After adding sodium citrate, the reaction is only 20 minutes, and the reaction time is too short, so that the amount of silver particles synthesized is too small; on the other hand, Since the reaction temperature is too high, the silver particles are rapidly formed, so that the silver particles are not adsorbed on the PS latex particles, so that the surface of the entire PS latex particles cannot be covered, and the surface of some of the PS latex particles is bare. Further testing, if the reaction time after adding the sodium citrate to the step (5) was extended to 30 minutes, similar results were obtained (not shown). Therefore, it is necessary to test different conditions.

Embodiment 4

Referring to Table 3, the synthesis steps of the nano silver particle-containing polystyrene latex particles in this embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) mixing 0.3 g of silver nitrate (AgNO ₃ ) with 15 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually becomes a goose yellow solution) ) to form a mixed solution and act for 1.5 hours; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (5.82 g of sodium citrate dissolved in 30 g of deionized water), continue the reaction for 30 minutes The solution was slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles was obtained. For the results observed by a transmission electron microscope (TEM), please refer to the third figure. Since the amount of silver nitrate and sodium citrate is too much, and the reaction is carried out for 1.5 hours after adding silver nitrate, the reaction takes a long time, so the reaction produces too much silver. So many silvers are gathered together.

Embodiment 5

Referring to Table 4, the synthetic steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) mixing 0.3 g of silver nitrate (AgNO ₃ ) with 15 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually becomes a goose yellow solution) ), to form a mixed solution, and for 1 hour; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (5.82 grams of sodium citrate dissolved in 30 grams of deionized water), continue the reaction for 30 minutes The solution was slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles was obtained. The results of observation by a transmission electron microscope (TEM) are shown in the fourth figure. Since the amount of silver nitrate and sodium citrate is excessively added, the reaction generates too much silver, so that many silver are aggregated.

Embodiment 6

Referring to Table 5, the synthetic steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) 0.1g of silver nitrate (AgNO ₃ ) is mixed with 5g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 95 ° C (the reaction tank solution gradually becomes a goose yellow solution). ) to form a mixed solution and act for 1 hour; (5) after cooling the mixed solution to 85 ° C, then add an aqueous solution of sodium citrate (1.94 g of sodium citrate dissolved in 10 g of deionized water), continue the reaction for 30 minutes The solution is slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the average particle diameter of the nano silver particles is 5 ~100nm. For the results observed by a transmission electron microscope (TEM), please refer to the fifth figure, because the appropriate amount of silver nitrate is added during the synthesis, and the reaction time is appropriate, so an appropriate amount of silver is formed, and because the reaction time is long, Therefore, the silver particles can have sufficient time to adsorb on the PS latex particles, so that the surface of the generated PS latex particles is uniformly covered with silver particles.

Example 7: Minimum inhibitory concentration (MIC) test

The nano-silver particle-containing polystyrene latex particles prepared in Example 6 were subjected to a bacteriostatic test to find the minimum inhibitory concentration (MIC) of the nano-silver particle-containing polystyrene latex particles. The "minimum inhibitory concentration" is the minimum sample concentration value that can inhibit the growth of quantitative test strains in 90% of the medium. The lower the MIC value, the better the bacteriostatic effect of the sample. In this example, Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli were used for experiments. Add different concentrations (0~0.020%) of antibacterial samples (including nano silver particle polystyrene latex particles) to the sterile culture tube, and then add 1c.c. Nutrient broth or TSB medium and known strains. The bacterial liquid was uniformly mixed; then, it was shaken and cultured in an incubator at 37 ° C for one day. After culturing, the suspension of the cultivating tube is clarified, and the appropriate ten-fold dilution method is applied to the agar vegetable plate medium for uniform coating. After culturing according to the appropriate growth conditions, the number of colony production is observed and calculated. MIC value.

The results are shown in the sixth figure. The nano-silver-containing polystyrene latex particles prepared in Example 6 have a bacteriostatic effect, and the minimum inhibitory concentrations for Staphylococcus aureus and Escherichia coli are 0.0075% and 0.011%, respectively.

Since the polystyrene latex particles obtained by the present invention have silver particles uniformly coated on the surface of the polystyrene latex particles, they have a good bacteriostatic effect, and since the silver particles are firmly attached to the polystyrene latex particles The surface will not be arbitrarily separated. Therefore, the addition of nano-silver particle polystyrene latex particles to cosmetics can not only replace the addition of traditional preservatives, but also solve the problem that tiny nano silver enters human cells through the skin, and can make the silver particles It achieves nano-scale dispersion and enhances its antibacterial effect.

In summary, the nano-silver particle-containing polymer latex particle composition of the present invention can achieve the intended use efficiency by the above-disclosed examples, and the present invention has not been disclosed before the application. It has fully complied with the requirements and requirements of the Patent Law.爰Issuing an application for a patent for invention in accordance with the law, and asking for a review, and granting a patent, is truly sensible.

The illustrations and descriptions of the present invention are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; those skilled in the art, which are characterized by the scope of the present invention, Equivalent variations or modifications are considered to be within the scope of the design of the invention.

Claims (7)

A polymer latex particle composition containing uniform distribution of nano silver particles, comprising polymer latex particles and nano silver particles dispersed on the surface of the polymer latex particles, wherein the polymer latex particles have a diameter of 390- 990 nm, the diameter of the nano silver particles is 5-100 nm, and the weight percentage of the polymer latex particles and the nano silver particles is 1000:1 to 1:1; wherein the composition is prepared by: 3.84 by weight 26 g of the polymer latex particle suspension was uniformly mixed with 5.1 g of a 1.96% by weight aqueous solution of silver nitrate (AgNO ₃ ) to form a mixed solution, and allowed to act at a temperature of 95 ° C for 1 hour; and the mixed solution was cooled to 80 ° C, Further, 11.94 g of a 16.25% by weight aqueous solution of sodium citrate was added to the mixed solution for 0.5 hour to obtain a polymer latex particle composition having a surface coated with nano silver particles. The polymer latex particle composition containing uniformly distributed nano silver particles according to claim 1, wherein the composition has a spherical structure or an elliptical structure. The polymer latex particle composition containing uniform distribution of nano silver particles according to claim 1, wherein the composition is for inhibiting growth of Gram-positive bacteria, Gram-negative bacteria and fungi. The polymer latex particle composition containing uniformly distributed nano silver particles according to claim 1, wherein the polymer latex particles are polystyrene latex particles and polymethylmethacrylate. Latex particles, poly-n-butyl methacrylate latex particles, latex particles of styrene and methyl methacrylate copolymer, latex particles of styrene and n-butyl methacrylate copolymer, Or latex particles of a copolymer of methyl methacrylate and n-butyl methacrylate. The polymer latex particle composition containing uniform distribution of nano silver particles according to claim 4, wherein the polymer latex particles are polystyrene latex particles. The polymer latex particle composition containing uniform distribution of nano silver particles as described in claim 1 is used for a cosmetic raw material composition and a pharmaceutical composition. The use of a polymer latex particle composition containing uniformly distributed nano silver particles according to claim 1 for the preparation of a cosmetic raw material and an antibacterial agent for a pharmaceutical composition for inhibiting Staphylococcus aureus ) and Escherichia coli , and the minimum inhibitory concentrations for Staphylococcus aureus and Escherichia coli are 0.0075% and 0.011%, respectively.